CRYSTALLIZATION OF POLY(ARYL ETHER KETONE KETONE) COPOLYMERS CONTAINING TEREPHTHALATE/ISOPHTHALATE MOIETIES

In a previous study, we have investigated the structure, crystallization, and morphology of poly(aryl ether ketone ketone), PEKK, copolymers prepared from diphenyl ether (DPE), terephthalic acid (T), and isophthalic acid (I) with T/I ratios from 100/0 to 50/50. These materials were considered as having -DPE-T-DPE-T- (TT) and/or -DPE-T-DPE-I- (TI) ''phthalate diads.'' In this work, we continue the study of this copolymer series with six different T/I ratios (40/60, 30/70, 20/80, 15/85, 10/90, and 0/100), which are viewed as having TI and/or -DPE-I-DPE-I- (II) ''diads.'' The I moieties (1,3-linked isomers) were always found to be incorporated in the crystals and acted as ''entropy or symmetry'' defects that effectively decreased the equilibrium melting temperature T-m(0) and the rate of crystallization. However, the retardation of crystallization in PEKK 0/100 (the homopolymer with pure II diads) was significantly less than expected, which was attributed to the segregation of I moieties between the chains leading to a reduction of total entropy in the unit cells. The evidence of segmental segregation in PEKK 0/100 was seen in x-ray diffraction patterns, where several extra reflections were seen that could only be indexed by the published unit cell modified with a larger c-axis dimension (3.048 nm, corresponding to the length of six phenyl residues or 1.524 nm, the length of three phenyl residues). The composition of 15/85 was found to have the lowest value of T-m(0) and the slowest crystallization rate. Upon heating, the ''II'' crystals (T/I from 30/70 to 0/100) exhibited the conventional double-melting behavior rather than the triple-melting behavior as in the ''TI'' crystals (50/50 to 40/60). No indication of the second polymorph form 2 was found in ''II'' crystals. (C) 1994 John Wiley and Sons, Inc.